Amide derivatives and process of making same



Patented Au 31, 1948 2,448,125 AMIDE nnnrva'rrvas AND raocass OF MAKINGSAME Richard Sallmann, Gelterkinden, and cm: Graenacher, Riehen,Switzerland, anignora to Clba Limited, a Swiu ilrm No Drawing.Application February 4, 1944, 80- rial No. 521,146. In Switzerland March26,

16 Claims. (01. zoo-404.5

The present invention relates to the manufacture of new amidederivatives by reacting amides containing at least one hydrogen atomattached to at least one amide nitrogen atom, particularly such amideswhich contain at least three carbon atoms, formaldehyde and salts ofammonia orsalts of primary amines with one another, if-

desired in the presence of an acid.

It is particularly advantageous to react the amide, for example aprimary amide, with the formaldehyde to form at first a N-methylolcompound, and then allowing this compound to react in a second stagewith an ammonium salt or a salt of a primary amine. if desired withaddition of an-acid. These N-methylol compounds of the amides are eitherknown or can be easily prepared according to analogous processes bytreating the amides dissolved in solvents, for instance water, alcohol,acetone. glacial acetic acid, benzene, pyridine and mixtures thereof,with formaldehyde, preferably at a moderately raised temperature and, ifnecessary, in the presence of condensing agents such as potash,trimethylamine or hydrogen chloride.

The reaction of the amides with formaldehyde and the ammonium or aminesalts is performed preferably in the heat and in the presenceofsolvents, such as methanol, ethanol, acetone-4f necessary with additionof acids, such as acetic acid, formic acid or hydrogen chloride. It isparticularly advantageous to carry out the reaction in concentrated.water-soluble organic acids, such as glacial acetic acid, for example at70- 100 C. The procedure may also be similar when applying themodification of the present process referred to in the openingparagraphs of the specification-reacting the amide with formaldehyde toform the methylol compound and allowing this compound to act on theammonium or amine salt. It is appropriate touse more than 1 mol'. offormaldehyde for each amide group, for example 3 mols.

The formaldehyde to be used in the present process is applied preferablyin the form ofits polymeric modifications for example in the formofpara-formaldehyde,

The amides which are used in this process may be derived from carboxylicacids as well as from sulfonic acids, further from ammonia and its basicmono-substitution products. They may represent, for example, carboxylicacid amides (primary amides or amides mono-substituted inv the amidegroup), urethanes, ureas, hydrazides,

. further suliamides.

example, amides which are derived from allphatic, aromatic,aliphatic-aromatic, cycloaliphatic and heterocyclic carboxylic acids.Among these are named: formic acid, acetic acid. propionic acid, acrylicacid, butyric acid, caprylic acid, lauric acid. coco nut fatty acid,palmitic acid, stearic acid, oleic acid, linoleic acid, hardened whaleoil fatty acid, adipinic acid, further benzoic acid, naphthoic acid,para-stearoylaminobenzoic acid, hexahydrobenzoic acid,tetrahydronaphthylracetic acid, resin acids or naphthenic acids, such asabietic acid, further chloroacetic acid, chloromethylbenzoic acid,chloroproplonic acid, glycollic acid. As starting materials there arealso suitable the N-substitution products resulting from the amides ofthe foregoing compilation which still contain at least one hydrogen atomlinked to the nitrogen atom, such as N-methyl-, ethyl-, hydroxyethyl-,dihydroxypropyl-lauric acid amide. Products possessing particularlyvaluable properties are obtained when using as starting materialsprimary amides of fatty acids with at least 12 carbon atoms. If theacids from which the amides to be used as starting materials are deriveddo not already contain 3 carbon atoms, it is advantageous to start fromsuch N-m'oncsubstitution products of these amides which contain at least3 carbon atoms. As starting materials there may further be mentionedcyclic amides, such as phthalimide and diketopiperazine. Asamides of theurea group there may be mentioned, for example, monoethyl-, monophenyl-,monododecyl-, monooctadecyl-, N:-N-didodecyl urea; as amides oftheurethane group for example octadecylurethane, further diurethanes, suchas methylene-dioctadecylurethane. As amides of the hydrazide group theremay be used for example the hydrazides corresponding to the aboveindicated amides, such as lauric' acid hydrazide. As amides of thesulfamide group there may be named for example replaced by a hydrocarbonradical which may also be substituted; in ammonia, however, the N-atom 3is linked with 3 hydrogen atoms. Ammonia and primary amines have commonproperties: they possess both the basic atom grouping NHaand form saltswith acids, both with inorganic and organic acids.

As ammonium salts, that is salts or ammonia, there may be used ammoniumsalts of organic or inorganic acids, such as ammonium acetate, ammoniumformate or ammonium chloride.

Among the salts of the primary amines there are named the following:salts, e. g.acetates or formates of aliphatic monoor polyvalent amines,the carbon chain of which may also contain substituents such ashydroxy-groups, for example, salts of methylor ethylamine, further saltsof butylor amylamines, salts of ethylenediamine, ofdiethylaminoethylamine or of polyalkylenepolyamines, e. g. ofpolyethylenepolyamines, moreover salts of hydroxyalkylamines e.g. saltsof monoethanol'amine, of hydroxypropylor hydroxybutylamines, ofpolyalkylenepolyamines containing hydroxyalkyl groups; salts of monoorpolyvalent aromatic amines, such as aniline, paradimethylaminoaniline,ortho-, metaor para-phenylenediamine; salts of cycloaliphatic monoorpolyvalent amines, such as cyciohexylamine,hexahydroortho-phenylenediamine. In case salts of diprimary diamines areused, 1 or 2 mols. of amide may be used for 1 mol. of diprimary diamine.

The constitution of the products obtained by the present process couldnot be ascertained and formulas for these products cannot, therefore, besupplied. Howeventhere is no doubt that the products of the inventioncontain the atomic grouping -C v iil' -CH N for instance,

CH N- -CHi-N l 01' 0 CnHrr-C NI'CHI-III CH1 O1 0 Cn n Nevertheless, theproducts can be fully characterized only by reference to theirmanufacturing processes. They may be designated as products obtained bythe process which comprises condensing amides containing at least 3carbon atoms and at least one hydrogen atom united to an amide nitrogenatom with formaldehyde and with salts of ammonia compounds in which atleast one nitrogen atom, besides being linked with hydrogen atoms, isconnected with at most one substituent, which products, in the form oftheir salts with low molecular aliphatic carboxylic acids are liquid tosolid substances which are soluble in water and are split up byprolonged boiling with hydrochloric acid.

The products of the present invention are soluble in water in the formof their salts with acids, and may find application as textileassistants. Particularly valuable are those products which tion, but arenot to be regarded as limiting it in any way, the parts being by weight:

Example 1 7 parts of ammoniumacetate and 14.1 parts of stearic acidamideare dissolved in 10 parts of glacial acetic acid at 70-80 C., whereupon5 parts of para-formaldehyde are added to this reaction mixture, whilethoroughly stirring, the temperature of the reaction mass rising to 95C. with generation of heat. ature begins to drop, the solution ismaintained at a temperature of 90-l00 C. by external heat supply,whereupon the reaction is complete after 10-15 minutes, a sample of thereaction solution, mixed with little formic acid, being clearly Isoluble in water without precipitating the starting material any longer.After distilling the glacial acetic acid in a vacuum, the residue isstirred with water and simultaneously rendered alkaline with causticsoda solution. The base which is completely insoluble in water isfiltered off, washed and dried. The new base is obtained as a colorless,solid fatty mass which is easily soluble in organic solvents. Theformate which is soluble in water but decomposes on prolonged boiling isobtained by dissolving the base in formic acid. The salts of the baseare split of! even more rapidly with mineral acidsin the heat, byprecipitating water-insoluble products.

The procedure is similar when using coconut fatty acid amide instead ofstearic acid amide.

Example 2 15 parts of ammonium acetate are dissolved in 40 parts byvolume of glacial acetic acid, whereupon 30 parts of coconut fatty acidmethylolamide are added at -90" C., while stirring. After the latter iscompletely dissolved, 10 parts of para-formaldehyde are added to thereaction mixture at 70-80 C. and the reaction mass is maintained at thistemperature, while stirring. After about 30 minutes a sample thereof,mixed with little formic acid, is clearly soluble in water. As soon asthis state is reached, the glacial acetic acid is distilled ofi in avacuum, the residue is thoroughly stirred with dilute caustic sodasolution, distilled off, washed with water until the reaction is nolonger alkaline, and dried. A solid, fatty mass is obtained whichdissolves in dilute acids with formation of strongly foaming solutions,and which is decomposed on boiling, especially with dilute mineralacids, with precipi- Example 3 4 parts of a monomethylamine acetatesolution in glacial acetic acid containing 25 percent. of base arediluted with 20 parts by volume of glacial As soon as the temper-.

. I acetic acid, whereupon 8 parts of methylol stearic acid amide areadded at Til-80 C. while stirring. After the latter has dissolved to aclear solution, 2 parts of para-formaldehyde are added to the reactionmixture which is then stirred at the indicated temperature until asample thereof is clear- 1y soluble in dilute acetic acid or formicacid,

which is the case after about 90 minutes. The product is worked up asdescribed'in Example 1, whereby the new base is obtained as a whitepowder which is soluble in dilute acids.

. 6,- oi! the glacial acetic acid in a vacuum. the residue is taken upin water, the solution is rendered feebly alkaline with caustic soda.solution and the product is precipitated with common salt, filtered anddried. There results a yellowish colored powder which is easily solublein dilute acids, the solutions of which possessing pronounced softeningThe strongly foaming solutions of these acids starting material, wherebya yellowish colored semi-solid base is obtained which has similarproperties like the stearic acid derivative obtained according to theabove example.

Example 4 9.5 parts of stearic acid methylolamide are introduced in astream of nitrogen at 50-60 C., while stirring, into a solution of 3.6parts of freshly distilled ortho-phenylene d-iamine in 25 parts ofglacial acetic acid, and when all has dissolved there are added 4 partsof para-formaldehyde at 70-'l5 C. The reaction mixture is heated forabout 2 hours, while stirring. to 70-80'C., whereupon a sample of thereaction mixture, to which some formic acid has been added, is clearlysoluble in water. The glacial acetic acid is distilled off in a vacuum,the residue is stirred with water and dilute caustic soda solution,filtered and washed with water until the reaction is neutral. The newbase is obtained as a white fatty powder which is soluble in diluteacidswith formation of foaming solutions.

A similar product which is also soluble in water is obtained whenworking as described in the above example, but starting from 2.16 partof ortho-phenylene diamine and condensing with 12.4 parts of methylolstearic acid amide.

' Example 5 properties.

Example 7 6 parts of cyclohexylamine and parts by volume of glacialacetic acid are reacted, as described in Example 3, with 6 parts ofstearic acid methylolamide and 3 parts of para-formaldehyde, whereby anew base soluble in dilute acids is obtained.

- as in Example 3.

12.6 parts of methylol stearic acid amide and s Examp 6 3 parts ofmonoethanolamine are dissolved in 20 parts by volume'of glacial aceticacid, where upon 10 parts of stearic acid methylolamide are introducedat TO-75 C. When the latter has completely dissolved there are added 5parts of para-- formaldehyde and the reaction mixture is main tained at70-75 C. while stirring, until a sample of the same is soluble in water.Aiter distillinl Example 8 A new condensation product is obtainedaccording to the process described in Example 3 by using the followingcomponents:

.5.4 parts of para-amlnodimethylan'iline dissolved in 25 parts by volumeof glacial acetic acid are mixed with 9.4 parts of stearic acidmethylolamide and 2 parts of para-formaldehyde. After heating for 2hours the reaction mixture is worked up in the usual manner, whereby ayellow colored base is obtained which is easily dissolved in diluteacids. r

Example 9 5.5 parts of coconut fatty acid hydrazide and 4 parts ofpara-formaldehyde are added at 60- '10- C. to a solution of 1 part ofmonomethylamine in 23 parts by volume of glacial acetic acid.

The reaction mixture isheated to 75430 C., while acetic acid and arerapidly'decomposed after addition of mineral. acid, especially'onheating, with precipitation of insoluble products.

Example 10 9.8 parts of 4-nitro-methylolbenzamide and then 3 parts ofpara-formaldehyde are added at lo- C. to a solution of 1.7 parts ofmonomethylamine in 25 parts by volume of acetic acid. The reactionmixture is kept for about /2 hour at the indicated temperature,whereupon a sample of the same is clearly solubledn acidified water.After distilling off the acetic acid in "a vacuum, there remains ayellowish colored, honey-like, viscous mass. The aqueous solutions ofwhich are fairly rapidly decomposed on heating with mineral acids, whilesplitting of! sparin'gly soluble products.

- Example 11 Q parts of stearic acid monomethylamide are introduced at8090 C., while stirring, into a solution of 1 'part of monomethylaminein 3 parts by volume of glacial acetic acid, and when all has dissolved,there are added 4 parts of paraformaldehyde. After the reaction haslasted for V hour at the above temperature, a sample is nearly clearlysoluble in water. The reaction mass is worked up as describedin Example3. The properties of the product correspond to those of the productobtained according to Example 3.

Example 12- Rayon can be softened in the following manner: Viscose rayonyarn is handled for V hour in an aqueous solution containing per liter0.03 gram of the product described in Example 1, the ratio of goods toliquor bjeing 1:30. The material is then centrifuged and dried. Therayon treated in such a manner has an extraordinarily soft,

flowing feel.

What we claim is: 1. A process for the manufacture of an amidederivative. which comprises condensing 1 mol of amide nitrogen atom withat least 2 mols of v formaldehyde and with 1 mol of a salt of ammonia atatemperature of at least 70 C. and in a solvent medium.

3. A process for the manufacture of an amide derivative, which comprisescondensing 1 mol of a primary amide of a fatty acid containing at least12 carbon atoms with at least 2 mols of formaldehyde and with 1 mol of asalt of ammonia at a temperature of at least 70 C. and in a solventmedium.

4. A process for the manufacture of an amide derivative, which comprisescondensing 1 mol of stearic acid amide with at least 2 mols of formaLdehyde and with 1 mol of ammonium acetate at a. temperature of at least70 C. and in presence of an acid.

5. A process for the manufacture of an amide derivative, which comprisescondensin 1 mol of an amide containing at least 12 carbon atoms and atleast one hydrogen atom united to an amldenitrogen atom with at least 2mols of formaldehyde and with 1 mol of a salt of a primary aminecontaining at least one primary amino group at a temperature of at least70 C. and in a. solvent medium.

6. A process for the manufacture of an amide derivative, which comprisescondensing 1 mol of an N-methylolamide of a primary amide containingatleast 12 carbon atoms and with 1 mol of a salt of a primary aminecontaining at least one primary amino group at a temperature of at least70" C. in a solvent medium containing at least 1 mol of formaldehyde.

7. A process for the manufacture of an amide derivative, which comprisescondensing 1 mol of an N-methylclamide of a primary amide of a fattyacid containnig at least 12 carbon atoms and with 1 mol of a salt of a.primary amine containing at least one primary amino group at atemperature of at least 70 C. in a solvent in dium containing at least 1mol of formaldehyde.

8. A process for the. manufacture of an amide derivative, whichcomprises condensing 1 mol of an N-methylolamide of a primary amide of afatty acid containing at least 12 carbon.atoms and with at least half 9.mol of a salt of a diprimary amine at a temperature of at least 70 C. ina solvent medium containing at least 1 mol of formaldehyde.

,9. A process for the manufacture of an amide derivative, whichcomprises condensing 1 mol of stearic acid N-methylolamlde with 1 mol ofmethyl amine acetate at a temperature of at least 70 C. in presence ofacetic acid and at least 2 mols of formaldehyde.

10. A process for the manufacture of an amide derivative, whichcomprises condensing 1 mol of stearic acid N-methylolamide with 1 mol ofethlyene diamine acetate at a temperature of at least 70 C. in presenceof acetic acid and at least 2 mols of formaldehyde.

11. A product obtained by condensing 1 mol of an amide containing atleast 12 carbon atoms and at least one hydrogen atom united to an amidenitrogen atom with at least 2 mols of formaldehyde and with 1 mol of amember selected from the-group consisting of salts of ammonia and saltsof primary amines at a temperature of at least 70 C. and in a solventmedium.

. 12. The product obtained by condensing 1 mol of stearicacid amide withat least 2 mols of form'- aldehyde and with 1 mol of ammonium acetate ata temperature of at least 70 C. and in presence of an acid. 1

I 13. The'product obtained by condensing 1 mol of an amide containing atleast 12 carbon atoms and at least one hydrogen atom united to an amidenitrogen atom with at least 2 mols of formaldehyde and with 1 mol of asalt of a primary amine containing at least one primary amino group at atemperature of at least 70 C. and in a solvent'medium.

14. The product obtained by condensing 1 mol of an N-methylolamide of aprimary amide of a fatty acid containing at least 12 carbon atoms andwith at least half 9. mol of a salt of a dlprimary amine at atemperature of at least 70 C. in a solvent medium containing at least 1mol of formaldehyde.

15. The product obtained by condensing 1 mol of stearic acidN-methylolamide with 1 mol of methyl amine acetate at a temperature ofat least 70 C. in presence of acetic acid and at least 2 mols offormaldehyde.

16. The product obtained by condensing 1 mol of stearic acidN-methylolamide with 1 mol of ethylene diamine acetate at a temperatureof at least 70 C. in presence of acetic acid and at least 2 mols offormaldehyde.

RICHARD SALIMANN. CHARLES GRAENACHER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,952,008 Bruson Mar. 20, 19342,075,109 Friedrich Mar. 30, 1937 2,200,452 Kosslinger May 14, 19402,278,417 Baldwin et a1. Apr. 7, 1942 2,304,156 Engelmann et al. Dec. 8,1942 FOREIGN PATENTS Number Country Date 500,110 Great Britain Jan. 30,1939

